Stabilization of physical configurations in cellulosic yarns,fabrics and garments through reaction with polyfunctional sulfone or sulfonium compounds



STABILIZATION or rnYsicAL CONFIGURA- TIONS IN CELLULOSIC YARNS, FABRICS AND cannrs rnnouorr nnAcrioN US. Cl. 8-120 20 Claims ABSTRACT OF THE DISCLOSURE Cellulosic textile materials are reacted with polyfunctional sulfone or sulfonium compounds under conditions of alkaline catalysis in a swollen state and thereafter heated. Polyfunctional sulfone or sulfonium-modified cellulosic textile materials are treated with a solution of alkaline catalyst, placed in the desired configuration and thereafter heated. The process lends itself to the delayed curing of yarns, fabrics and garments.

This is a continuation-in-part of our earlier filed copending applications Ser. No. 261,833 filed Feb. 28, 1963 and Ser. No. 292,727 filed July 3, 1963, both applications being now abandoned.

The present invention relates to methods for imparting an essentially permanent configuration to fibrous materials containing or derived from cellulose, and more particularly, methods by which cellulosic yarns, fabrics and other textile products manufactured from cellulosic fibers or yarns can be treated to impart an essentially permanent shape or configuration.

The resilience and wrinkle recovery of textile materials are among the most important performance properties and often determine the extent of commercial success for the material. These properties are particularly significant in the case of clothing because it is widely recognized that consumers prefer garments which resist the formation of wrinkles and creases during service and have the ability to recover from wrinkling. In addition, there are numerous other areas where such properties are important. Textile materials employed for curtains, drapery, upholstery and similar applications require good properties of shape retention of siiflicient durability to withstand long service.

Cellulosic fibers have long been known and widely em? ployed for clothing and the like and, even after the development of synthetic fibers, have continued to remain important for a large number of applications because of various factors such as availability, durability, low cost, comfort properties and other desirable features.

However, because fibers of the cellulosic family, e.g., cotton, linen, rayon, modified rayons are inherently less resilient than some of the man-made hydrophobic fibers, textiles made from them generally have a tendency toward wrinkling and creasing in service.

In an effort to improve the performance properties of textile materials made from cellulosic fibers and to overcome their disadvantages, numerous processes have been developed whereby materials composed wholly or mainly of cellulose are chemically modified by reacting the cellulose molecules with polyfunctional reagents. As a result of these methods, resilience and crease resistance of products made from cellulosic fibers are notably improved. It is believed that the reaction between polyfunctional 3,540,836 Patented Nov. 17, 1970 reagents and the cellulose molecules results in crosslinking of cellulosic chains. Among the desirable properties which may be imparted to cellulosic textiles by such crosslinking reactions are, for example, improved resilience, improved dimensional stability and, especially in the case of fabrics, improved crease recovery in the dry state and in the wet state. These improved properties greatly extend and in crease the usefulness of cellulosic materials. The crosslinking of cellulose in textile structures permits their use in articles of manufacture where resilience, dimensional stability in laundering, recovery from creasing and fiat drying properties after laundering are required.

Many polyfunctional crosslinking reagents have been employed and have achieved commercial acceptance, for example, nitrogenous thermosetting resins containing N- oxymethyl reactive groups have been extensively used in the treatment of cellulosic fabrics. A more recent development which has attracted considerable attention is the treatment of cellulosic materials with polyfunctional sulfur containing compounds such as divinyl sulfone in the manner described in Schoene et al. Patent 2,524,399. Reagents in this category have been widely recognized as achieving excellent results in the improvement of crease resistance. In addition, they overcome certain disadvantages which are incurred in the use of other textile treating materials such as nitrogenous materials. The hydrolytie stability and resistance to bleaching of nitrogenous thermosetting resins is generally limited, and the sulfur containing compounds overcome these shortcomings.

It is generally known in the art that cellulosic textile materials such as yarns and fabrics, can be set in any desired configuration by a crosslinking reaction. That is to say, the cellulosic textile material to tends to return to the particular configuration in which it is held while carrying out a chemical reaction or crosslinking of the cellulosic molecules with the functional groups of the reagents. If the crosslinking reaction is carried out while the textile material is held fiat, the fiat configuration will be fixed in the fabric and the fabric will acquire a tendency to return to the fiat state after being subjected to deformation. If, on the other hand, the crosslinking reaction takes place while the fabric is shaped in a different configuration such as a pleat, then the pleat configuration will be fixed, and the fabric will tend to return to the pleat configuration after deformation. Applied to yarns, the crosslinking reaction can proceed while the yarn is held in a highly twisted state whereupon the highly twisted configuration will be fixed. Then by applying an untwisting or detwisting force, bulk, stretch and crimp characteristics will be imparted to the treated yarns. The permanence of the effect achieved by such treatment depends primarily, of course, on the specific reagent employed in the crosslinking reaction.

The tendency of chemically modified cellulosic fabrics and yarns to return to the configuration in which they are held While the crosslinking reaction takes place is referred to in the textile treating art as the memory of the material. As a result of this memory one finds, for example, that fabrics obtained by carrying out crosslinking reactions while the cellulosic fabrics are held fiat and free of wrinkles do, indeed, show a tendency to return to a flat configuration. Such fabrics are commonly called wash and wear or flat drying fabrics, and have been widely used in the textile industry. Certain difficulties have, however, been encountered with articles manufactured from such fabrics.

As explained above, when the fabrics are held fiat during crosslinking, they tend to return to the flat state after being subjected to deformation. It is because of this tendency, that garments manufactured from these wash and wear, crease resistant cellulosic fabrics cannot easily be creased by ironing. When creases or pleats are desired in a manufactured article such as a garment or in draperies, for example, the fabrics which have been treated to become crease resistant will resist the formation of the pleats and creases in the course of ironing. Creases imparted by prolonged ironing are lost in service and/or laundering operations more readily than in the case of untreated cellulosic fabrics.

There are many types of articles in which it is desirable to have pleats and creases that are durable in wear and after laundering operations as, for example, in the case of trousers, pleated skirts, curtains and similar manufactured goods. Durable creases can be imparted by heating (e.g., with a hot iron) to fabrics made from synthetic fibers which are thermoplastic in nature such as polyamide, polyester, polyacrylonitrile, and polyolefin fibers. Similarly, bulked and crimped yarn have been manufactured from thermoplastic fibers by heat setting the yarn, in a predetermined configuration. However, processes suitable for thermoplastic materials have not been applicable to yarns which consist solely or mainly of cellulosic fibers because of the non-thermoplastic nature of cellulosic fibers. Since cellulosic fibers, and particularly cotton, are preferred for many end-uses, it has been recognized in the industry that there is a need for developing methods by which permanent creases and pleats can be imparted to manufactured goods such as garments made from crease resistant cellulosic fabrics and also methods by which cellulosic yarns and fabrics of improved resilience can be treated to impart to them permanent bulk, crimp and stretch characteristics. Many attempts have been made to make cellulosic textiles suitable for apparel and other purposes wherein durable creases are necessary and desirable.

One such approach has involved what is known in the art as the delayed cure technique. This refers to a process wherein the cellulosic fabric is impregnated with a polyfunctional reagent and catalyst While at the textile mill. The crosslinking reaction is subsequently induced after the cellulosic textiles have been made up into garments or other manufactured goods. Such methods encounter a number of difficulties in operation. For example, if the formulation employed is not sufiiciently stable to storage, reaction with the fi-bers will take place while the textile is still on the roll and the memory of the material will be set in that configuration. If, on the other hand, the formulation applied is sufficiently stable so that curing does not occur on the roll, then drastic curing conditions will usually be required to induce the crosslinking reaction to take place. Furthermore, before the textile material is cured, care must be exercised in handling the textile material impregnated with the reagent and catalyst. For example, the textile cannot be washed because the reagent and catalyst are soluble in water before curing and would thus be washed out and removed.

Another process employed heretofore is one wherein the cellulosic textiles are treated with resinous materials in the presence of an acid catalyst, and cured in a fiat configuration in the textile mill. Processes for imparting a permanent crease to these materials involve breaking and reforming the chemical bonds between the fabric and reagent after the garment has been manufactured by applying acid forming catalysts in selected areas and heating to induce partial hydrolysis. Such a process is difficult to control and, in addition, dimensional changes in some areas of the fabric produce changes in shape which are manifested, for example, by puckering.

Hence, it would be highly desirable to provide chemically modified cellulosic textile materials which can be produced in the textile mills, which can be knitted or woven in the case of yarn and can be cut and sewn and made up into the garments and, in the case of fabrics, which subsequently can be permanently shaped, creased and pleated, if and when desired.

Accordingly, it is the object of this invention to avoid the shortcomings of prior known processes for imparting a durable configuration to manufactured goods containing cellulosic textile materials.

It is a further object of this invention to provide methods for imparting a durable configuration to crease and wrinkle resistant fabrics after such fabrics have been made into manufactured goods.

Still another object of this invention is to provide methods for quickly, easily and efficiently forming pleats or creases in cellulosic fabrics which have been treated with crease resistance compositions and which normally resist the formation of creases and wrinkles.

It is a further object of this invention to provide methods for imparting a durable configuration to yarns while maintaining ease of handling in weaving and knitting.

It is a further object of this invention to provide methods for chemically modifying cellulosic yarns with polyfunctional reagents in order to impart permanent bulk, twist configuration crimp and stretch characteristics.

In attaining the objects of this invention, one feature resides in treating a cellulosic material with polyfunctional crosslinking agents in the presence of a swelling agent and thereafter heating the chemically modified cellulosic material in order to change its properties. By controlling the time and temperature of the heating treatment, a preferred selection of properties may be ob tained in the final product.

A further feature of this invention resides in treating a chemically modified cellulosic material with a catalyst; imparting the desired, predetermined, configuration to the cellulosic material; and thereafter applying heat to the material while in the desired configuration, thereby giving the cellulosic material a memory for the newly formed configuration.

Another feature of this invention resides in treating a textile material containing chemically modified cellulosic molecules with an aqueous alkaline catalyst solution, and heating, thereby further modifying the structure of the cellulosic molecules, and imparting the desired predetermined properties or configuration to the textile material.

A further feature of this invention resides in treating fabrics or garments woven or knitted from chemically modified cellulosic yarns with a catalyst, and curing to obtain a product with permanent stretch and recovery properties.

Other objects, features and advantages of the invention will become apparent from the following description of the invention.

It has now been discovered that textile yarns and fabrics containing cellulosic materials can be chemically modified by treatment with certain polyfunctional crosslinking agents in the presence of a swelling agent and subsequently be permanently set in any desired configuration by heating in the presence of an alkaline catalyst.

More particularly, it has been discovered that the properties of textiles containing cellulosic materials treated with polyfunctional compounds in the presence of a swelling agent, such as the treatment of textile materials with polyfunctional sulfone compounds in the presence of water according to the processes disclosed in the copending application, Ser. No. 826,133 filed July 10, 1959 and now abandoned, Ser. No. 41,805 filed July 20, 1960 and now abandoned, Ser. No. 79,988 filed Jan. 3, 1961, Ser. No. 107,893 filed May 5, 1961 now US. Pat. 3,441,- 954 and Ser. No. 189,689 filed Apr. 24, 1962 and now abandoned, can be changed in a durable and permanent manner by heating in the presence of an alkaline catalyst, without the addition of further crosslinking agents, reactants or other finishing agents. The products obtained by the processes disclosed in US. Patent Nos. 2,524,399 and 3,068,123 may also be treated according to the disclosure of this invention described herein.

The cellulosic textile materials which can be treated to impart durable, permanent deformation thereto are those which have been reacted with polyfunctional sulfurcontaining compounds in the presence of water, steam or other suitable swelling medium and in the presence of alkali. Among suitable polyfunctional reagents are those which are disclosed in the aforementioned applications, Ser. Nos. 826,133 and 79,988 and which can be represented by the general formula I. YCHCHS 2(QSO2)11CHCHY I i 1 31 R2 R3 wherein R, R R R are selected from the group consisting of hydrogen and lower alkyl, Q represents a divalent organic radical containing more than 2 carbon atoms, n has a value of to 1, and Y represents a polar residue derived from a reagent of weak nucleophilic character such as the cation of a Weak base (e.g., pyridinium, isoquinolinium and the like) and the anion of a strong acid (e.g., SSO Na or thiosulfate, OSO Na or sulfate, OCOH or acetate and the like). Nucleophilic character is defined as the tendency to donate electrons or share them with a foreign nucleus, see Gilman0rganic Chemistry, 2d ed., vol. II, page 1859. More specifically, Y can be derived from a tertiary amine having an ionization constant lower than about l0 or from a polybasic inorganic acid, an organic or organically substituted inorganic acid having an ionization constant greater than The following are specific examples of compounds which come within the scope of Formula I:

where M is selected from the group consisting of alkali metal and ammonium;

MO SSCH CH SO CH CH SSO- M where M has the same meaning as in the previous formula: H COCOCH CH SO CH CH 'OCOCH (C H NCH CH SOCH CH NC H 2X- Where X is halogen;

where X is halogen.

Further examples of polyfunctional sulfone compounds are those described in the aforementioned application Ser. No. 107,893 which are of the general formula:

where n is an integer number and has a value of 2 to}, A is selected from the group consisting of oxygen and nitrogen, and does not have any hydrogen atoms attached to it, R is a lower alkyl group, Q is an organic radical in which the number of unsatisfied valences is equal to n, and b has a value from 0 to l but if A is oxygen, then b is 0.

Included by the above generic formula are the following compounds:

omorn CHg=CHSOzCHgCHgN NcH2oH2so2oH=orr2 ongorn CH2CHSO2OH2OH2NCO-NCHgCHzSOzCH CIh CH2 CH3 and N(CH CH OCH CH SO CH CH Additional polyfunctional sulfone compounds which may be employed to chemically modify cellulosic materials are those set out in the aforementioned application Ser. No. 189,689 and correspond to the formula:

CHFCHSO RSO CH CH where R is a divalent aliphatic radical selected from the group consisting of (a) C H Where n is equal to 3 to 10 and ( a 2a b a 2a where a is 2 to 4, b is 1 to 4 and Y is a member selected from the group consisting of oxygen, S0 and NR where R is selected from the group consisting of hydrogen and lower alkyl radicals.

Included in the above group of compounds are the following:

CH CHZSO CH CH and Still further examples of polyfunctional sulfone compounds which may be employed to chemically modify cellulosic materials are compounds of the formula:

ROCH CH SO [QSO CH CH OR wherein R and R are selected from the group consisting of hydrogen and lower alkyl,

Q is a divalent organic radical selected from the group consisting of aliphatic radicals containing at least three carbon atoms, aromatic radicals and alkylaromatic radicals, and

y is selected from zero and 1.

Further examples of these compounds are disclosed in our aforementioned application Ser. No. 41,805, filed July 11, 1960.

Among the suitable sulfone compounds coming within the formula set forth hereinabove are bis(beta-oxethy1 sulfones), i.e., both the hydroxy and alkoxy sulfones such as and their analogues and homologues, and the like. Any suitable sulfone can be used alone or in mixtures with others in the practice of this invention.

The reaction of compounds of the above formula RO CH CH SO [QSO CH CH OR' with cellulose represents an unexpected feature of the present invention. While it has been suggested, for example, in the aforementioned application No. 41,805 to crosslink cellulose with the above polyfunctional reagents in a drying atmosphere, it is unexpected to get any reaction at all in the presence of a swelling agent, as in the case of steam with sulfones which react by elimination of water or alcohol. It is also surprising that, although reaction does take place between the sulfone and the cellulosic material that is being treated as shown by standard analytical methods, the properties of the steamed product are vastly different from those of a cured product pre pared in accordance with the anhydrous process referred to hereinabove. This is true even at the same percentage levels of fixed sulfur. The steamed product is capable of further reaction when heated in a drying atmosphere. Subsequent operations effected on the material do not result in loss of sulfone which is attached thereto and moreover, when the steamed product is cured in the presence of a catalyst only, it becomes crosslinked and exhibits excellent recovery and crease retention properties similar to those of products prepared from fabrics treated with the other sulfones discussed above.

Further polyfunctional sulfone compounds which are used to impart crease resistance to the cellulosic materials are described in the above mentioned applications, Ser. Nos. 826,133, 79,988, 107,893 and 189,689, the entire disclosures of which are incorporated herein by reference.

Divinyl sulfone, CH =CHSO CH:CH may also be employed to chemically modify cellulosic textile yarns and fibers according to the process described in US. Pat. No. 2,524,399. The modified textile materials may then be employed according to the methods disclosed herein.

In addition, textiles rendered crease resistant by treatment with polyfunctional sulfonium compounds corresponding to the formula in which R is selected from the group consisting of alkyl, substituted alkyl and CH CH X, where X is a polar residue derived from a polybasic acid, may also be further modified according to the methods of the present invention to obtain a durable, permanent configuration. Included in the general formula given above are the following sulfonium compounds:

+S/CHZCH2O S Orwhere M is selected from the group consisting of sodium, potassium and lithium and R has the meaning given above.

In all the above instances the modified cellulosic textile materials are obtained by reacting polyfunctional sulfurcontaining reagents with cellulose under suitable condi tions in the presence of a swelling agent for cellulose such as water, steam, or other swelling agents. The modified cellulosic materials so obtained are suitable starting materials for practicing the process of the present invention in that they can be further reacted by heating in the presence of an alkaline catalyst, and thus can be permanently set in any desired configuration by carrying out this heating step after the predetermined configuration has been imparted.

After a textile material such as, for example, a cotton fabric has been chemically modified according to the teachings of the above referred to processes with any of the above polyfunctional sulfur-containing reagents, it may be cut, sewn and manufactured into an article such as a skirt, blouse or a pair of trousers. According to one feature of the present invention, a mild alkaline catalyst is deposited on the fabric either prior to or after manufacturing the garment. The garment is then shaped into the desired crease, pleat, fold or other configuration and is held in this configuration while heat is applied to the garment by any convenient means. The creases and pleats imparted to the garment become fixed in a durable, permanent manner. It is also possible, if desired, to hold the textile in a straight, smooth or flat configuration during the heating step whereby the textile will be set in the flat condition and the crease recovery of the fabric will be markedly improved over what it was previously.

Yarns containing cellulosic materials which have been treated to improve their resilience by any of the above referred to processes are then subsequently treated according to the methods of this invention to impart durable and essentially permanent configurations thereto. For example, the yarn material may be contacted with an aqueous alkaline catalyst solution before or after they are twisted, bulked, crimped or knitted. The yarns are then heated While they are held in the desired configuration until the configuration is set or fixed. By this process a durable, permanent twist, bulk or crimp can be imparted to the yarns, The twisting, bulking or crimping of the yarn can be imparted by any of the suitable commercial units available for such purposes.

The methods of this invention also provide a convenient way to make fabrics having stretch characteristics. In operation, a cellulosic yarn is first twisted and chemically modified by contacting the twisted yarns with any of the above referred to polyfunctional sulfur-containing reagents in the presence of a swelling agent and an al kaline catalyst. The dry yarns can be detwisted at any convenient time and, when dry, they will tend to remain detwisted, thereby facilitating the weaving or knitting step wherein the yarns are woven or knitted into a suitable fabric. Upon Wetting the fabric made from the chemically modified yarns, a relaxation of the yarns, and dimensional changes in the fabric can be induced. The fabric can then be treated with a suitable catalyst and heated while the yarns are in the relaxed condition. The heating will stabilize the relaxed configuration of the yarns and result in a fabric having good permanent stretch properties both in the wet and dry condition.

Since it is difiicult to weave or knit a fabric from highly twisted yarns, one advantage of the present method for making stretch cellulosic fabrics resides in the ease of manufacturing a fabric from yarns of normal twist. Another advantage resides in the convenience of setting the desired relaxed configuration by heating after the fabric has been made. The overall effect of this aspect of the invention is to permanently fix the configuration of the modified cellulosic yarns contained in a fabric, thereby producing a textile which has excellent permanent stretch and recovery properties, always returning to the relaxed condition after it is stretched, either wet or dry.

The textile materials which can be treated according to the methods of the present invention are those which consist solely or in part of cellulosic fibers. The term cellulosic fibers as used herein includes but is not limited to cotton, linen, viscose rayon, cuprammonium rayon, and the like. Modified cellulosic fibers such as cellulose acetate, cross-linked rayon and the like are also included as suitable for the purposes of this invention providing that a substantial number of free hydroxyl groups are present in the cellulosic polymer.

When blends of fibers are employed in the textile which is treated according to the methods of the present invention, the cellulosic materials, should be present in an amount of at least 20% based on the weight of the textile treated, and preferably about 30% or higher. Although textile materials containing such amounts of cellulosic materials in mixtures or blends with other fibers can be treated, the results observed by practicing the methods of the present invention are more readily apparent and more useful when the cellulose content of the textile is higher.

In order to impart the desired shape, the chemically modified textile material is treated with an alkaline catalyst solution containing an alkaline compound which can be any compound capable of yielding a pH of 8 or higher in a 1% aqueous solution. Such materials as the carbonates, bicarbonates, acetates and phosphates of alkali metals including sodium, potassium and lithium are very effective for these purposes. In addition, organic bases such as the tertiary amines and quaternary ammonium hydroxides can also be employed. Mixtures of alkaline catalyst may also be employed. Although the hydroxides and silicates of alkaline metals including sodium, potassium and lithium are also operative, they are somewhat less desirable than the aforementioned alkaline compounds since heating of the cellulosic fibers in the presence of the alkali hydroxides in order to set the desired configuration to the textile product can result in discoloration of the textile material. Of course, the alkali hydroxides can be used wherever such discoloration is not objectionable. For example, in the case of textiles which have been dyed a dark color considerations of discoloration would not be as pertinent as in the case of lighter shades. Where textiles have been pretreated to prevent discoloration as, for example, with sodium borohydride, the alkali hydroxides may be employed.

The amount of alkaline catalyst present when the chemically modified cellulose is subjected to elevated temperatures in order to set the predetermined configuration is adjusted to the level such that a mild alkaline medium is produced. Hence, in general, amounts varying from about 0.5 to based on the weight of the modified cellulosic material treated may be employed, The optimum amount should be selected by experimentations and would depend upon the cellulosic textile which is treated, on the alkaline compound selected as the catalyst, on the specific configuration in which the cellulosic textile is to be set, and also on the time and temperature selected for the curing or setting operation.

After the aqueous alkaline catalyst solution is'applied and the cellulosic textile material shaped in the desired configuration, the textile material is exposed to elevated temperatures while held in the configuration. The conditions of heating will vary over a considerable range but the temperature should preferably be higher than about 200 F. It has been found that temperatures in the range of 250 F. to 400 F. yield excellent results, although higher temperatures may be employed. When yarns are processed in continuous equipment considerably higher temperatures of the order of 700 to 750 F. are employed because residence time is short. The sources of the heat which is applied to the textile material can be any one of conventional means such as steaming, pressing or baking.

One of the outstanding advantages of the present invention is that it enables a tailor, for example, to take a finished garment and to pad it with the dilute alkaline catalyst solution and then simply place it on the conventional tailors press whereby the desired creases and folds are set in the durable and permanent configuration. The procedure can be even further simplified by padding a fabric with the dilute alkaline solution while the material is still at the mill or manufacturing plant. Then all the tailor or presser need do is to impart the proper fold or crease configuration to the garment and heat. This considerably enhances the commercial usefulness and applicability of the present process. The only critical factor in the operation being that the textile should be kept in the desired configuration during the heating step.

The time of heating which is necessary to achieve the desired results depends on other processing variables, but heating time varying from several seconds to several minutes are usually sufficient to achieve the desired results.

In the examples which follow, the polyfunctional reagents used to modify the cellulosic yarns and fabrics so as to obtain the enhanced properties and so as to render them amenable to permanent deformation according to the novel methods of the present invention are among those shown in the formulae above. However, it must be understood that cellulosic textiles modified in the presence of water or other suitable swelling agents under alkaline conditions with other polyfunctional compounds may also be employed.

The test methods referred to in the examples are as follows:

Crease recoveryMonsanto Method ASTMD12956T Wash/wear ratingTechnical Manual AATCC-V. 38,

pp. B-88 to B92 (No. 881961-T) Crease retentionAmerican Dyestufi Reporter, Dec. 25,

1961, pp. 1017 to 1019 Laundering procedure-AATCC 88l961-T Test III.

EXAMPLE 1 154 grams of anhydrous bis-beta-hydroxyethyl sulfone were warmed to 5060 C. and 160 grams of liquid stabilized sulfuric anhydride (B.P. 44.8 C.marketed under the trade name Sulfan by the General Chemical Division of the Allied Chemical Co.) were added dropwise with cooling and vigorous mechanical stirring, care being taken to keep the reaction temperature at 50- 60 C. throughout the addition which required 2 /2 hours.

After completing the addition, the reaction mixture was stirred at 5060 C. for one additional hour, then allowed to cool to room temperature. The entire reaction mixture (314 grams) was poured onto 310 grams of ice and water, and 1.5 grams of sodium acetate were added. The aqueous solution was neutralized to pH 4-5 by adding sodium carbonate (powder) in small portions with stirring. The resulting aqueous solution, containing 37% active ingredient (calculated) was pale yellow and could be decolorized by a brief treatment with charcoaL The analysis of the active ingredient in solution was carried out by determining the amount of sodium hydroxide consumed. Eq. wt. calcd. 179, found 189. The product is the disodium salt of the bis-sulfuric acid ester of bis-betahydroxyethyl sulfone, hereinafter referred to as BHES disulfate.

EXAMPLE 2 Aqueous solutions containing 22% and 15% of the sulfone prepared in Example 1 were prepared. Small amounts (2.3 and 1.8% respectively) of 35% active nonionic polyethylene emulsion were added to these solutions. Samples of cotton broadcloth were treated with these solutions on a laboratory padder (the wet pickup was l00%), framed to the original dimensions and dried in a forced draft oven at 200 F. The sample treated with 22% sulfone was then padded with a 9% NaOH solution, and the sample treated with 15% sulfone was padded with a 6.6% NaOH solution, so as to yield a ratio of about 1.1 equivalents of NaOH to 1 equivalent of reagent on the two samples.

After padding with the alkali, the samples were framed, covered with polyethylene sheets to prevent evaporation of water, allowed to stand at room temperature for 30 minutes, and thoroughly washed.

The properties of the treated broadcloth samples are compared with those of our untreated control sample in Table I.

In the following tables, the values given for wet and dry crease recovery are in degrees and are based on a scale where 360 is a maximum value. The higher the number of degrees the greater is the tendency of the fabric to recover from wrinkling. The values included for wash and wear rating and crease retention rating are based on a scale where a rating of 1 denotes a textile that is worse in appearance and a rating of 5 denotes a textile having the best appearance.

When the sample treated with 15% sulfone was padded with a 2% solution of potassium bicarbonate and cured for 2 minutes at 325 F., the dry crease recovery was increased from 200 to 271, and the wash/wear rating after tumble drying was increased from 2.3 to 5.0. The sulfur content of the treated fabric, the wet crease recovery and the wash/ wear rating in line drying were unchanged.

EXAMPLE 3 Samples of broadcloth fabric processed with 15 sulfone according to the procedure of Example 2 were immersed in a 3% solution of potassium bicarbonate, and centrifuged to remove excess solution. One sample (A) was then framed and heated smooth and flat in a forced draft oven at 380 F. for 1 minute; a portion of the sample after heating (A') was creased, and ironed creased with the iron set at 300 for six minutes; a second sample B) was creased, ironed creased with the iron set at 300 F. for 6 minutes; a third sample (C) was pleated, and ironed in the pleated configuration with the iron set at 300 F. for 8 minutes. The samples were tested for crease recovery, crease retention in laundering and wash/ wear rating after laundering (L). The results obtained are shown in Table II. (Each laundering was in a household washing machine at 140 F. It is apparent from the results shown in Table II that creases imparted after the heating step (Sample A) are easily removed in laundering, while creases imparted during the heating step (Samples B and C) are permanent to laundering.

TABLE II Sample A A B C Grease recovery:

Dry 255 256 251 254 276 270 268 278 Crease retention rating:

After 1L, line dried 1 5. 0 5. 0 After L, tumble dried 1 0 5. 0 5. 0 Wash/wear rating:

After 5L, line dried 4. 5 4. 6 3. 8 4. 0 After 5L, tumble dried 4. 5 4. 8 5. 0 4. 5

In Examples 2 and 3 the second reaction in the sulfone treated fabric may be controlled by varying the amount of catalyst or temperature or time. The reaction may be thus controlled to alter the ratio of wet/dry crease recovery in the final product.

EXAMPLE 4 A 100% cotton twill fabric having a weight of 8 ounces per square yard and a width of 42 inches was padded on commercial equipment with an aqueous solution containing 18% of the sulfone prepared according to the procedure of Example 1. The wet pickup was 66%, and

TABLE III Crease recovery:

Dry 182 Wet 276 Wash/wear rating:

After 1L, line dried 4.2 After 5L, tumble dried 3.7

The sulfur content of the fabric was 0.89%. Trousers were manufactured from this finished fabric. The trousers were immersed in a 2% solution of potassium carbonate, carefully pressed for 8 minutes in a Hoffmann press. The creases which were set in the trousers in this manner still had an appearance rating of 5.0 after 10 machine launderings at 140 F.

EXAMPLE 5 A sample of two ply cotton yarn (size 18.5/2 cotton count) was treated with a 15 solution of the sulfone of Example 1 by circulation in conventional yarn dyeing equipment of the sulfone solution through a package of the yarn wound on a perforated tube. The excess liquor was removed by centrifuge to provide a wet pickup of (15% sulfone) on the yarn, after which the package was thoroughly dried in a forced draft oven at 200 F. A solution of 5% NaOH was then circulated through the yarn alternately in each direction, at room temperature for 5 minutes. As the reaction proceeded, the concentration of NaOH was maintained approximately constant by gradual addition. When the reaction was completed as evidenced by no further change in NaOH concentration, the NaOH was displaced by circulation of a 2% solution of KiHCO The yarn package was then extracted by centrifuge in order to provide a wet pickup of 100% (2% KHCO on the yarn, after which the yarn package was thoroughly dried in a forced draft oven at 200 F.

The yarn which has now been modified in the wet state and on which an alkaline catalyst has been deposited was then processed on conventional equipment used to impart false twist to thermoplastic staple fiber yarns, designed to impart a false twist to yarn material. The heating chamber of a commercial apparatus known as a Fluflon false twist unit was set at 700 (F., the false twist spindle speed was 6350 r.p.m. and the yarn speed 6 yards per minute. After passage through the apparatus the yarn was permanently deformed and resembled in appearance, stretchability and recovery, a nylon or polyester staple yarn processed on the same equipment. The residual catalyst was allowed to remain on the yarn until it was convenient to scour following weaving. The fabric woven therefrom after scouring showed excellent stretch and recovery properties.

EXAMPLE 6 A sample of multifilament viscose rayon (75 45/ 2T5) was processed as in Example 5 with the exception that a 22% solution of BHES disulfate was used and KOH was used as the catalyst for the wet reaction in order to minimize degradation of the viscose yarn. The false twist was applied on another commercial apparatus known as the Superloft unit manufactured by the Leesona Corp. The heating chamber was set at 750 F, the yarn speed was 16 yards per minute, and the spindle speed was 40,000 rpm. The processed yarn was permanently deformed and resembled in appearance, stretchability and recovery a nylon or polyester multifilament yarn processed on the same equipment.

EXAMPLE 7 A sample of two ply cotton yarn which was twisted to 30 turns per inch (t.p.i.) S ply twist was treated with a 15% solution of the sulfone employed in Example 1 impregnated with a 5% NaOH solution according to the process described in Example 5. After this treatment the yarn sample was washed and dried. The yarn was then twisted 40 t.p.i. in the opposite direction and woven into a fabric. The fabric was then wet with a 2% solution of KHCO and allowed to relax in the wet condition. Thereafter, the fabric width, stretch and recovery properties were set by completely curing the fabric at about 300 F.

EXAMPLE 8 A sample of multiiilament viscose rayon (75/45/2TS) was twisted to 30 t.p.i. S twist and treated with a 15 solution of BHES disulfate prepared according to Example 1. The rayon was impregnated with a 5% KOH solution following the procedure of Example 5 after which the sample was washed and dried. The modified rayon was then twisted 40 t.p.i. in the opposite direction and thereafter woven into a fabric. A 2% solution of potassium bicarbonate was employed to wet the woven fabric, which was allowed to relax in wet condition. The fabric width, stretch and recovery properties were permanently set by curing the fabric at about 300 F.

EXAMPLE 9' A sample of 18.5/2 cotton yarn was continuously treated with BHES disulfate and sodium hydroxide on the modified Flufion unit using steam. The yarns were subsequently woven into a fabric. The fabric was then wet with a 2% solution of potassium bicarbonate and allowed to relax in the wet condition. Thereafter, the fabric was cured at about 300 F. to completely set the fabric width, stretch and recovery properties.

EXAMPLE Samples of 18.5/2 ply cotton yarns were continuously treated with BHES disulfate and NaOH on the modified Flufion false twist unit employing steam. The yarns which were thus chemically modified in the wet condition were then continuously treated with potassium bicarbonate on the modified Fluflon unit in order to permanently set the dry twist configuration. By varying the false twist setting during both the wet and dry reactions, it is possible to produce yarns with different stretch and bulk properties.

EXAMPLE 1 1 A sample of single ply cotton yarn 18.5/ 1) was treated with a solution of the sulfone of Example 1 by circulation in conventional yarn dyeing equivalent of the sulfone solution through a package of the yarn wound on a perforated tube. Excess liquor was removed by centrifuge to provide a wet pickup of 100% (15 sulfone) in the single yarn. The yarn package was thoroughly dried in a forced draft oven at 200 F. A solution of 5% NaOH was then circulated through the yarn alternately in each direction, at room temperature for 5 minutes. As the reaction proceeded the concentration of NaOH was maintained approximately constant by gradual addition. After completion of the reaction, a 2% solution of KHCO was circulated to displace the NaOH. The yarn package was then extracted by centrifuging to pro vide a wet pickup of 100% (2% KHCO in the yarn, after which the yarn package was thoroughly dried in a forced draft oven at 200 F.

The yarn which has now been reacted in the wet state and on which an alkaline catalyst has been deposited was then processed on equipment used to impart false twist to single ply fibers such as that fully described in copending application Ser. No. 224,371 filed Sept. 18, 1962, now abandoned. The heating chamber was set at 700 F.,

the false twist spindle speed was 6350 rpm. and the yarn speed was 6 y.p.m. After passage through the apparatus the single yarn was permanently deformed and resembled in appearance, stretchability and recovery properties, a nylon or polyester staple yarn processed on the same equipment. The residual catalyst was allowed to remain on the yarn until it was convenient to scour following weaving. The fabric woven from this yarn showed excellent properties, particularly stretch and recovery.

EXAMPLE 12 14 yarns are reacted in the wet condition, they are continuously treated with KHCO on the modified Fluflon unit. Yarns with different stretch and bulk properties were obtained by varying the false twist setting during both wet and dry cros-slinking.

EXAMPLE 13 An x 80 cotton print cloth fabric was padded with an aqueous solution of gms. of his (beta-hydroxyethyl) sulfone and 65 gms. (0.5 equivalent) of potassium bicarbonate per liter. The wet pickup was 100 percent. The impregnated fabric was dried to a moisture content of 4 to 10 percent. The treated fabric was then subjected to an atmosphere of saturated steam for 3 minutes, washed in hot water and dried. The sample was divided into two parts. The crease recovery angle at this stage was 169 (dry) and 171 (wet). One part of this fabric was impregnated with a 6.5 percent solution of potassium bicarbonate, squeezed through rollers to give 100 percent Wet pickup, dried and cured in a forced draft oven at C., washed and dried. The crease recovery angle was 241 for both the dry and wet fabric. Another sample was similarly padded with the bicarbonate solution, dried, creased and cured. Crease retention ratings of 5.0 were obtained after one and five launderings followed by tumble drying. Untreated fabrics, after steaming, were creased and pressed. The crease retention rat ing after one laundering is 1.0.

The second part of the fabric after steaming and washing was machine laundered five times at 60 C. and dried. The crease recovery angles, wet and dry, at this stage, were the same as those obtained after steaming. This sample was then impregnated with a 6.5 percent solution of potassium bicarbonate, squeezed through rollers to give 100 percent wet pickup, dried and cured in a forced draft oven at 165 C., washed and dried. The crease recovery angle was 238 for both the dry and wet fabric.

EXAMPLE 14 An 80 x 80 cotton print cloth fabric was treated as in Example 13 except that 33 gms. (0.25 equivalent) of potassium bicarbonate per liter were used with the sulfone and steaming was carried out for 5 minutes. The following results were obtained.

Crease recovery angle After steaming:

An 80 x 80 cotton print cloth fabric was treated as in Example 13 except that 260 gms. (2.0 equivalents) of potassium bicarbonate per liter were used with the sulfone and steaming was carried out for 5 minutes. The following results were obtained:

Crease recovery angle After steaming:

Dry 179 Wet 194 After curing:

Dry 250 Wet 243 EXAMPLE 16 An 80 x 80 cotton print cloth fabric was treated as in Example 13 except that 26 gms. (0.5 equivalent) of sodium hydroxide per liter were used with the sulfone and steaming was carried out for minutes. The following results were obtained:

Crease recovery angle After steaming:

Dry 180 Wet 183 After curing:

Dry 253 Wet 240 EXAMPLE 17 An 80 x 80 cotton fabric was treated as in Example 13 except that 200 grns. of bis (beta-hydroxyethyl) sulfone and 130 gms. potassium bicarbonate per liter were used and steaming was carried out for 2 minutes. The following results were obtained:

Crease recovery EXAMPLE 18 An 8 02. cotton twill fabric was impregnated with an aqueous solution of 145 gms. bis (beta-hydroxyethyl) sulfone and 94 gms. (0.5 equivalent) of potassium bicarbonate per liter, squeezed to give a wet pickup of 70 percent and dried to a moisture content of 4 to percent. The treated sample was divided into two parts. One part (a) was put in contact with saturated steam at 100- 103 C. for 3 minutes. The second part (b) was steamed in like manner for 5 minutes. Both samples were then washed in hot water and dried. A 9.4 percent aqueous solution of potassium bicarbonate was prepared and applied to the two samples. The impregnated fabrics were squeezed to give a 70 percent Wet pickup and then dried. They were creased, pressed and cured in the creased configuration at 150 C. in a forced draft oven. Control fabrics, after steaming, were also creased and pressed. The following results Were obtained:

A fabric sample, after steaming and washing, was analyzed for sulfur. A similar sample was likewise analyzed after creasing and curing. Analysis showed that the percentage of sulfur remained unchanged.

EXAMPLE 19 A rayon challis was treated as in Example 13 except that 200 gms. of his (beta-hydroxyethyl) sulfone and gms. potassium bicarbonate per liter were used. Moreover, the sample was divided into two parts (a) and (b) each of which was subjected to steam for 3 minutes and 5 minutes, respectively. The following results were obtained:

Crease recovery angle Sample (a) Sample (1)) After After After After steaming curing steaming curing 1 Dry 181 240 129 201 Ollgmal "{Wet 194 239 188 237 Crease retention rating Sample (a) Sample (b) After After After After steaming curing steaming curing 1 laundering, tumble dried 1. 0 4. 5 1. 0 4. 5 5 launderings, tumble driecL 1. 0 5. 0 1. O 4. 0

EXAMPLE 20 A 2.8 oz. cotton dress fabric (90 x 80) was treated as in Example 13. After steaming, overpadding with the bicarbonate solution and subsequent drying, the fabric was pleated on a continuous pleating machine at a press temperature of C., using paper on both sides. The pleated fabric was then cured in a forced draft oven at C. The following results were obtained:

Crease recovery angle After steaming:

EXAMPLE 21 An 80 x 80 cotton print cloth fabric was treated as in Example 13 except that after steaming it Was divided into two parts. The first part (i) was left as is. The second part (ii) was overpadded and processed as in Example I.

Each of these pieces was divided into four parts and dyed as follows:

(a) A dye bath was prepared with 2.0 percent Superlite [Fast Yellow EFC (direct dye-Althouse Chemical Co.) with a liquor ratio of 30: 1. Swatches of (i) and (ii) were dyed by the standard procedure;

EXAMPLE 22 An 80 x 80 cotton print cloth fabric was treated as in Example 13 except that the 100 grns. of bis(beta-hydroxy ethyl) sulfone were replaced by 100 gms. of bis(hydroxyethyl sulfonyl) ethyl ether and using 33 gms. (0.5 equiva- 17 lent) of potassium bicarbonate per liter. The padded fabric was steamed for 5 minutes. The following results were obtained:

Crease recovery angle After steaming After curing Original "$3:

Crease retention EXAMPLE 23 An 8.0 02. cotton twill was treated as in Example 18 except that the 145 gms. of bis (beta-hydroxyethyl) sulfone were replaced by 100 gms. of bis(hydroxyethyl sulfonyl) ethyl ether and using 47 gms. (0.5 equivalent of potassium bicarbonate per liter. The dried fabric was steamed for 7 minutes. The following results were obtained:

(b) A dye bath was prepared with 1.0 percent Indanthrene Blue GP powder (Vat dyeGeneral Dyestutf Company) using caustic soda and sodium hydrosulfite. swatches of (i) and (ii) were dyed by the standard procedure;

(c) A dye bath was prepared with 1.0 percent Algosol Red lFBB-CF (Vat dye ester-General Dyestuif Company). Swatches of (i) and (ii) were dyed by the standard procedure;

(d) Swatches of (i) and (ii) were dyed with 1.0% Procion Brilliant Yellow 6GS (Reactive Dye-Irnperial Chemical Industries) using the pad batch method.

In all cases fabric (i) dyed to the same color weight as an untreated control dyed under the same conditions. The fabric (ii), however, gave only a 10 to 20 percent color yield. All the dyed samples were then impregnated with a 6.5 percent solution of potassium bicarbonate, dried, creased, pressed and cured in a forced draft oven at 150 C., in their creased configuration. The creased pieces were laundered five times and tumble dried. In every case the sample (ii) and the untreated controls gave a crease retention rating of 1.0 while the sample (i) rated between 4.5 and 5.0.

Crease retention rating After After steaming curing 1 laundering, tumble dried 1. 5.0 launderings, tumble dried 1.0 4. 8

EXAMPLE 24 A rayon challis was treated as in Example 13 except that the 100 gms. of bis(beta-hydroxyethyl)sulfone were replaced by 200 gms. of bis(hydroxyethyl sulfonylethyl) ether and using 65 gms. (0.5 equivalent) of potassium bicarbonate per liter. The dried fabric was steamed for 5 minutes. The following results were obtained:

Crease recovery angle After After steaming curing O O Ongmal 402%.: ii Eli Crease retention rating After After steaming curing 1 laundering tumble dried 1.0 5. 0 5 launderings tumble dried 1. 0 4. 3

The invention illustrated by the above examples thus provides a simple, efficient and highly advantageous method for imparting durable creases and pleats in arments which are made from cellulosic textile materials that have been modified by treatment with polyfunctional reagents. The textile materials are normally treated to carry out a reaction of the polyfunctional reagent with the cellulose at the textile mill and from there the textile material is shipped to the clothing manufacturer who makes up the garment employing the modified yarns or fabrics.

The present invention enables a tailor to impart to the completed garment permanent creases and pleats which will be retained after repeated launderings and in heavy usage by simply padding the garment with the dilute alkaline solution and placing the garment in a steamer, press or oven to set the desired configuration of the pleats or creases. If the catalyst has been previously applied, all that is necessary to permanently set the configuration is heat. N0 expensive equipment is necessary and no complicated impregnation and washing procedures are required.

Similarly, a manufacturer who buys cellulosic yarn from a textile mill where the yarn has already been treated to increase its resilience can knit the modified yarn into a garment to be set by heating, or he can follow the methods as disclosed in the foregoing examples and impart a permanent twist configuration to the yarn and produce from such yarn products with stretch characteristics.

EXAMPLE 25 A cotton twill fabric having a weight of 8 ounces per square yard was padded with an aqueous so ution containing bis-betahydroxyethyl sulfone (15%), potassium bicarbonate (10%), and Ansul Ether 181 (10%). (Ansul Ether 181 is a trademark of the Ansul Company for 2,5,8,11,14-pentaoxapentadecane, the dimethyl ether of tetraethylene glycol.) The wet pickup was 65%. Hence, the amount of bis-beta-hydroxyethyl sulfone actually deposited on the fabric in the padding operation was 10% based on the weight of the fabric. The fabric was dried at 180 F. for 5 minutes. Then it was cured at 250 F. for 60 seconds, after which time the fabric was allowed to cool to room temperature. In other to complete the first step in this example, the fabric was washed in water, dried, and stored for the second step. At this stage, crease recovery of the dry fabric was found to be 184 degrees of angle.

For the second step, teh fabric was overpadded with a solution of potassium bicarbonate so an additional 6.5% (based on the original weight of the fabric) of potassium bicarbonate was deposited on the fabric. The fabric was then dried pressed with a crease in it, and re-cured at 325 F. for seconds. The fabric resulting from this 2-step procedure was conditioned and tested at 70 F. with relative humidity at 65%. Results were as follows:

Crease recovery, dry 221 Crease recovery, wet 258 Crease retention:

After 1L, line dried 4.8 After L, line dried 4.8 After 1L, tumble dried 4.5 After 5L, tumble dried 5.0 Wash/ wear rating:

After 1L, line dried 4.0 After 5L, line dried 4.0 After 1L, tumble dried 4.5 After 5L, tumble dried 4.0

(L stands for laundering or launderings) Note that dry crease recovery angle of the fabric increased from 184 to 221 degrees through the processing of the second step, or a gain of 37 degrees in this important practical property.

EXAMPLE 26 The procedure and conditions of Example 25 were repeated with the same materials except for variations in the conditions of curing during the first step. As in EX- ample 25, in the second step the fabric was (1) overpadded so as to deposit an additional 6.5% (based on the original weight of the fabric) of potassium bicarbonate, (2) dried, (3) pressed, and (4) re-cured at 325 F. for 120 seconds. Results were as follows:

Curing temperature in the first step, degrees F 300 Curing time in the first step, sec 60 Crease recovery, dry, in the first step, degrees 196 Properties after the second step:

Crease recovery:

Dry degrees 217 Wet degrees 263 Crease retention:

after 1L, line dried after 5L, line dried after 1L, tumble dried. after 5L, tumble dried Wash/wear rating:

after 1L, line dried after 5L, line dried after 5L, tumble dired.-. Increase in crease recovery, dry, through use of the second step, degrees EXAMPLE 27 An 8-ounce all-cotton twill fabric was padded with an aqueous solution containing bis-beta-hydroxyethyl sulfone (15%), potassium bicarbonate (10% and polyethylene glycol 600 (10%). (Polyethylene glycol 600 is the trade name for a product consisting of closely related compounds of generic formula HO(CH CH O),,H having an average molecular weight of approximately 600.) The wet pick-up was 65%. The amount of bis-beta-hydroxyethyl sulfone deposited on the fabric was 10% based on the weight of the fabric. The fabric was dried at 180 F. for 5 minutes. Then it was cured at 250 F. for 60 seconds, after which the fabric was allowed to cool to room temperature. In completing the first step, the fabric was washed in water, dried, and stored in preparation for the second step. At this point, crease recovery (dry), angle was 173 degrees.

For the second step, the fabric was overpadded with a solution of potassium bicarbonate so as additional 6.5 (based on the weight of the original fabric) of potassium bicarbonate was deposited on the fabric. Then the sample was dried, pressed with a crease in it, and re-cured at 325 F. for 120 seconds. The fabric resulting from this 2-step procedure was conditioned and tested, both at F. and relative humidity 65 Results were as follows:

Crease recovery:

Dry 229 Wet 259 Crease retention:

After 1L, line dried 5.0 After 5L, line dried 4.5 After 1L, tumble dried 4.3 After 5L, tumble dried 4.0 Wash/ wear rating:

After 1L, line dried 4.0 After 5L, line dried 2.5 After 1L, tumble dried 4.3 After 5L, tumble dried 4.3

An appreciable gain in crease recovery (dry) was obtained through the use of the second step, namely 56 degrees of angle.

EXAMPLE 28 The procedure and conditions of Example 27 were repeated with the same materials except for variations in the conditions of curing during the first step. As in Example 27, in the second step the fabric was (1) overpadded so as to deposit an additional 6.5 (based on the weight of the original fabric) of potassium bicarbonate, (2) dried, (3) pressed, and (4) re-cured at 325 F. for 120 seconds. Results were as follows:

Curing temperature in the first step, degrees F 300 325 Curing time in the first step, sec 60 120 Crease recovery, dry, in the first step, degrees 200 190 Properties after the second step:

Crease recovery:

Dry, degrees 200 Wet, degrees 247 Crease retention:

after 1L, line dried 3. 8 3. 0 after 5L, line dried 3. 0 after 1L, tumble dried 3. 0 after 5L, tumble dried 4. 3 3. 8 Wash/wear rating:

after 1L, line dried 3. 5 3. 5 after 5L, line dried 3. 0 3. 3 after 1L, tumble dried 4. 0 4. 0 after 5L, tumble dried 4. 5 4. 5 Increase in crease recovery, dry, through use of second step, degrees 23 10 EXAMPLE 29 A cotton twill fabric having a weight of 8 ounces per square yard was padded with an aqueous solution containing bis-beta-hydroxyethyl sulfone (15 potas sium bicarbonate (10%), and 1-methyl-2-pyrrolidone (10% commonly called N-methylpyrrolidone. Based on the weight of the fabric, the amount of bis-beta-hydroxyethyl sulfone deposited on it was 10%. The fabric was dried at 180 F. for 5 minutes. Then it was cured at 300 F. for 60 seconds, after which the fabric was allowed to cool to room temperature. In completing the first step, the fabric was washed in water, dried, and stored in preparation for the second step. At this point, crease recovery angle (dry) was 209 degrees.

For the second step, the fabric was overpadded with a solution of potassium bicarbonate so an additional 6.5 (based on the weight of the original fabric) was deposited on the fabric. Then the sample was dried, pressed with a crease in it, and re-cured at 325 F. for seconds. The fabric resulting from the 2-step procedure was conditioned and tested at 70 F. with relative humidity at 65% Results were as follows:

Crease recovery:

Dry 224 Wet 265 Crease retention:

After 1L, line dried 4.0 After 5L, line dried 4.3 After 1L, tumble dried 3.8 After 5L, tumble dried 4.3 Wash/wear rating:

After 1L, line dried 4.3 After 5L, line dried 4.3 After 1L, tumble dried 4.3 After 5L, tumble dried 4.0

By means of the processing in the second step, crease recovery (dry) angle was improved by degrees.

EXAMPLE A 100% cotton twill fabric having a weight of 8 ounces per square yard was padded with an aqueous solution containing bis-beta-hydroxyethyl sulfone (15%), potassium bicarbonate (10%), and Polyox WSR (10%). (Polyox WSR is a trademark of Union Carbide for watersoluble resin of high molecular weight made by polymerizing ethylene oxide.) The wet pick-up was Based on the weight of the fabric, the amount of bis-betahydroxyethyl sulfone deposited on it was 10%. The fabric was dried at 180 F. for 5 minutes. Then it was cured at 300 F. for 60 seconds, after which the fabric was allowed to cool to room temperature. In completing the first step, the fabric was washed in water, dried, and stored in preparation for the second step. Crease recovery (dry) angle at this point was 212 degrees.

For the second step, the fabric was overpadded with a solution of potassium bicarbonate so an additional 6.5% (based on the weight of the original fabric) was deposited. Then the sample was dried, pressed with a crease in it, and re-cured at 325 F. for 120 seconds. The fabric resulting from the 2-step procedure was conditioned and tested at F. with relative humidity at 65%. Results were as follows:

Crease recovery:

Dry 233 Wet 266 Crease retention:

After 1L, line dried 4.3 After 5L, line dried 4.0 After 1L, tumble dried 4.0 After 5L, tumble dried 4.5 Wash/ wear rating:

After 1L, line dried 3.5 After 5L, line dried 3.0 After 1L, tumble dried 4.5 After 5L, tumble dried 4.5

By means of the second step, crease recovery of the dry fabric was increased, this time by 21 degrees.

It is understood that various other modifications will be apparent to and can readily be made by those skilled in the art without departing from the scope and spirit of this invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the description set forth herein but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention, including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains.

What is claimed is:

1. A process for imparting permanent configuration to cellulosic textile material comprising contacting said cellulosic textile material in the presence of saturated steam and an alkaline catalyst with sulfone having the formula wherein R and R are selected from the group consisting of hydrogen and lower alkyl,

Q is a divalent organic radical selected from the group consisting of aliphatic radicals containing at least three carbon atoms, aromatic radicals and alkylaromatic radicals, and

y is selected from zero and 1, arranging said cellulosic textile material in a desired configuration, exposing said cellulosic textile material to an elevated temperature of at least 200 F. in the absence of moisture and permanently fixing the arranged configuration in said cellulosic textile material.

2. A process according to claim 1 wherein the sulfone is bis (B-hydroxyethyl) sulfone.

3. A process according to claim 1 wherein the sulfone is B-hydroxyethyl fl-methoxyethyl sulfone.

4. A process according to claim 1 wherein the sulfone is bis(fi-hydroxyethyl sulfonylethyl) ether.

5. A process according to claim 1 wherein the sulfone is bis({3-hydroxyethyl sulfonyl) butane.

6. A process according to claim 1 wherein the sulfone is his (B-methoxyethyl sulfone).

7. A process as defined in claim 1 wherein the catalyst is sodium hydroxide.

8. A process as defined in claim 1 wherein the catalyst is sodium carbonate.

9. A process as defined in claim 1 wherein the catalyst is potassium bicarbonate.

10. A process for imparting permanent configuration to cellulosic textile material comprising contacting said cellulosic textile material in the presence of an alkaline catalyst with sulfone having the formula ROCH CH SO [QSO CH CH OR' wherein R and R are selected from the group consisting of hydrogen and lower alkyl,

Q is a divalent organic radical selected from the group consisting of aliphatic radicals containing at least three carbon atoms, aromatic radicals and alkylaromatic radicals, and

y is selected fro zero and 1, subjecting the material to an atmosphere of saturated steam for a time sufiicient to react the sulfone with the cellulosic material, removing the material from said atmosphere of steam, arranging said cellulosic textile material in a desired configuration, exposing said cellulosic textile material at an elevated temperature of at least 200 F. in the absence of moisture and permanently fixing the arranged configuratiOn in said cellulosic textile material.

11. The process of claim 10 further characterised in that the step of subjecting the material to an atmosphere of saturated steam is for a period of time in a range of about 3 seconds to about 20 minutes.

12. The process of claim 10 in which about 2.0 to 25.0 percent by weight of sulfone is employed based on the weight of said cellulosic textile material, the material is exposed to an atmosphere of saturated steam from about 3 seconds to about 20 minutes, the arranged material is exposed to a temperature in a range of about C. to 250 C., and the alkaline catalyst is employed in a range of about 0.05 to 2.5 equivalents by weight based on the equivalent weight of sulfone. 1

13. The process of claim 10 in which about 10.0 to 20.0 percent by weight of sulfone is employed based on the weight of said cellulosic textile material, the material is exposed to an atmosphere of saturated steam from about 12 seconds to about 10 minutes, the arranged material is exposed to a temperature in a range of about 23 120 C. to 250 C., and the alkaline catalyst is employed in a range of about 0.25 to 0.75 equivalents by weight based on the equivalent weight of sulfone.

14. The process of claim in which about 10.0 to 20.0 percent by weight of sulfone is employed based on the weight of said cellulosic textile material, the material is exposed to an atmosphere of saturated steam from about 3 to 7 minutes, the arranged material is exposed to a temperature in a range of about 120 C. to 250 C., and the alkaline catalyst is employed in a range of about 0.25 to 0.75 equivalents by weight based on the equivalent 'weight of sulfone.

15. The process of claim 10 further characterized in that the cellulosic textile material upon being removed from the atmosphere of saturated steam is washed to remove unreacted sulfone and catalyst therefrom and subsequently is contacted with additional alkaline catalyst.

16. A process as defined in claim wherein the steaming is carried out on a fabric and the curing is carried out on a finished garment.

17. A method of imparting an essentially permanent configuration to fibrous cellulosic material in the form of yarn which comprises reacting said yarn with a crosslinking agent in the presence of a swelling agent and an alkaline catalyst to thereby obtain a chemically modified cellulosic material, said crosslinking agent being selected from the group consisting of wherein R, R R and R are selected from the group consisting of hydrogen and lower alkyl,

Q is a divalent organic radical containing more than 2 carbon atoms,

n has a value of zero to 1,

Y represents a polar residue derived from a reagent of weak nucleophilic character selected from the group consisting of cations of Weak bases and anions of strong acids;

[a ornonzzoii wherein R is alkyl, substituted alkyl and CH CH X, and X is a polar residue derived from a polybasic acid;

(3) CH CH SO RSO CH=CH 24 wherein R is a divalent aliphatic radical selected from the group consisting of C H a a 2a b a 2awherein n is 3 to 10 and a is 2 to 4, b is 1 to 4 and Y is selected from the group consisting of oxygen, and

wherein n is an integer number and has a value of 2 Q is an organic radical in which the number of unsatisfied valences is equal to n,

(5) CH =CHSO CH=CH and (6) ROCH CH SO [QSO CH CH OR' wherein R and R are selected from the group consisting of hydrogen and lower alkyl,

Q is a divalent organic radical selected from the group consisting of aliphatic radicals containing at least three carbon atoms, aromatic radicals and alkylaromatic radicals, and

y is 0 or 1,

twisting said yarn to form a desired twist configuration and exposing the yarn to elevated temperatures of at least 200 F. in the presence of an alkaline catalyst while maintaining the yarn in the desired configuration to thereby set the desired twist configuration in the cellulsoic yarn.

18. The method of claim 17 wherein the yarn is cotton.

19. The method of claim 17 wherein the yarn is regenerated cellulose.

20. The modified yarn product produced by the method of claim 17.

References Cited Reeves et al. American Dyestufl? Reporter, vol. 48, No. 21, pp. 43-46, 50, Oct. 19, 1959.

GEORGE F. LESMES, Primary Examiner J. CANNON, Assistant Examiner U.S. Cl. X.R. 

